Diarylnonanoids and their glucosides from Erica cinerea

Article abstract of DOI:10.1016/j.tetlet.2011.01.108

The reinvestigation of Erica cinerea fresh aerial parts led to the isolation of two new diarylnonanoid aglycones along with their glucosides. From spectroscopic data, their structures were elucidated as rel-(3R,7R)-1,9-bis(p- hydroxyphenyl)-3,7-dihydroxynonan-5-one named ericanone, ericanone 3-β-d-glucoside, (3S)-3,7-anhydro-6,7-dehydroericanone and (3S)-3,7-anhydro-6,7-dehydroericanone 4′-β-d-glucoside. Contrary to the numerous diarylheptanoids more frequently distributed in the plant kingdom, the rare diarylnonanoids were previously restricted to the genus Myristica of the Myristicaceae plant family.

Full text of DOI:10.1016/j.tetlet.2011.01.108

Tetrahedron Letters 52 (2011) 1597–1600
Contents lists available at ScienceDirect
Tetrahedron Letters
journal homepage: www.elsevier.com/locate/tetlet
q
Diarylnonanoids and their glucosides from Erica cinerea
a
a,
⇑
b
a
a
Bachir Bennini , Albert J. Chulia , Mourad Kaouadji , Patrice Fondanèche , Daovy P. Allais
a
Laboratoire de Pharmacognosie, UPRES EA 4021 ‘Biomolécules et Thérapies Antitumorales’ Faculté de Pharmacie, 2, Rue Docteur Marcland F-87025 Limoges Cedex, France
Département de Chimie, Faculté des Sciences et Techniques 123, Avenue A. Thomas F-87060 Limoges Cedex, France
b
a r t i c l e i n f o
a b s t r a c t
Article history:
The reinvestigation of Erica cinerea fresh aerial parts led to the isolation of two new diarylnonanoid agly-
Received 24 November 2010
Revised 19 January 2011
Accepted 24 January 2011
Available online 1 February 2011
cones along with their glucosides. From spectroscopic data, their structures were elucidated as rel-
(
3R,7R)-1,9-bis(p-hydroxyphenyl)-3,7-dihydroxynonan-5-one named ericanone, ericanone 3-b-
D
-gluco-
-gluco-
0
side, (3S)-3,7-anhydro-6,7-dehydroericanone and (3S)-3,7-anhydro-6,7-dehydroericanone 4 -b-
D
side. Contrary to the numerous diarylheptanoids more frequently distributed in the plant kingdom, the
rare diarylnonanoids were previously restricted to the genus Myristica of the Myristicaceae plant family.
Ó 2011 Elsevier Ltd. All rights reserved.
Keywords:
Ericaceae
Erica cinerea
rel-(3R,7R)-1,9-Bis(p-hydroxyphenyl)-3,7-
dihydroxynonan-5-one
Ericanone
Ericanone 3-glucoside
(
2S)-2,6-Bis(p-hydroxyphenethyl)-2,3-
dihydropyran-4-one
(
(
3S)-3,7-Anhydro-6,7-dehydroericanone
3S)-3,7-Anhydro-6,7-dehydroericanone 4
0
glucoside
Our last studies on the acetone extract of fresh Erica cinerea L.
Five resonances (d 211.4, 68.1, 51.9, 40.5 and 32.0) corresponded to
a tetrasubstituted nonan-5-one chain (C-5: d 211.4) indicated by
one pair of equivalent oxymethines (d 68.1) and three pairs of
equivalent methylenes (d 51.9, 40.5 and 32.0). The remaining
aerial parts at the flowering stage, characterized flavonoid agly-
1
cones, glycosides, as well as an acylglycoside and a disulfate.
The same material extract was reinvestigated to deepen the phyto-
chemical content of this species. Based on partitioning with petrol,
dichloromethane and ethyl acetate successively, and then a multi-
step chromatographic treatment of the ethyl acetate soluble por-
tion, this process resulted in the isolation of aglycones 1 and 3
2
four peaks in the C sp shift range supported two symmetrical
0
00
0
00
0
00
p-hydroxyphenyls (C-1 ,1 : d 134.2; C-2 ,2 ,6 ,6 : d 130.4; C-
0
00
0
00
0
00
3 ,3 ,5 ,5 : d 116.2; C-4 ,4 : d 156.5). To comply with the substitu-
tion pattern of the C chain, each aromatic ring must be attached to
9
2
and the corresponding glucosides 2 and 4. Moreover, the two for-
one end as supported by the EIMS base peak at m/z 107 for p-
mer metabolites were also detected in the CH
2
Cl
2
extract among
hydroxybenzylium fragment-ion. Furthermore, the multiplicity of
the oxymethine proton pair in the H NMR spectrum (d 4.02, br
1
the major (E)- and (Z)-3-p-coumaroyltriterpenes. By spectroscopic
evidence including UV, MS as well as NMR, the basic structure of
the newly reported compounds was established as 1,9-diarylnona-
noid with either open or partly cyclized C chain, a higher homo-
9
logue of the well-known 1,7-diarylheptanoid backbone.
quint, J = 6.3 Hz), clearly indicated for each one to have four cou-
1
1
pling partners. This was also reflected in the H– H COSY spectrum
by the cross-peaks they displayed with two nuclei at d 2.61 and
2.56, respectively, and with two more at d 1.68. Thus, the oxygen
atoms must be linked to either C-2,8 or C-3,7. Parallely, although
unresolved, the complex H-1,9 multiplets (H-1a,9a: d 2.64 and H-
1b,9b: d 2.53) clearly excluded the presence of a tertiary carbon
in the immediate vicinity as depicted in the 2,8-dihydroxy alterna-
tive. Hence, the oxygen atoms of hydroxyl groups were attached to
C-3,7 and 1 was assigned the structure of 1,9-bis(p-hydroxy-
phenyl)-3,7-dihydroxynonan-5-one, a new natural product desig-
2
7
Compound 1 was isolated as a white amorphous powder, ½ ꢀ
a
D
ꢁ
14 (c 0.042, MeOH). It exhibited a UV spectrum consisting of
MeOH
max
one band at k
26 5
280 nm, and the molecular formula C21H O
supplied by HRESMS (found: 381.1673; calcd: 381.16779 for
+
13
[
M+Na] ). The C NMR spectrum (Table 1) made up by only nine
signals for C21, suggested well an apparent symmetrical structure.
1
13
q
nated as ericanone. A detailed analysis of the H– C HMBC
Part 11 in the series Phytochemistry of the Ericaceae.
⇑
Corresponding author. Tel: +33 5 55 43 58 34; fax: +33 5 55 43 59 10.
E-mail address: jose.chulia@unilim.fr (A.J. Chulia).
spectrum (Table 1) supported this 1,3,7,9-tetrasubstituted nonan-
5-one chain and corroborated assignments for all the 1H and
13
C
0
040-4039/$ - see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tetlet.2011.01.108

Table 1
1
3C NMR (125 MHz) and 1H NMR (500 MHz) data for diarylnonanoids 1 and 3 and their glucosides 2 and 4 in CD
OD (d ppm; J Hz)a
3
C/H
1
2
3
4
13C
32.0
1H
HMBC
13C
31.8
1H
HMBC
13C
31.3
1H
HMBC
13C
31.3
1H
HMBC
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
2
2.64 m
C-3; C-2 ,6
C-3; C-2 ,6
C-4; C-1
2.59 m
C-3; C-2 ,6
C-3; C-2 ,6
C-4; C-1
2.72 m
2.65 m
2.06 br ddt
C-3; C-2 ,6
C-3; C-2 ,6
C-4; C-1
2.72 m
2.65 m
2.06 br ddt
(14.2; 8.1; 6.1)
1.92 m
C-3; C-2 ,6
C-3; C-2 ,6
C-4; C-1
2
.53 m
40.5
1.68 dt (8.1; 6.7)
38.9
1.86 br hext (7.1)
.75 m
37.4
37.2
(
14.2; 8.1; 6.1)
0
0
0
1
C-4; C-1
C-1; C-5; C-1
1.91 m
4.30 ddt
C-4; C-1
C-1; C-5; C-7
C-4; C-1
C-1; C-5; C-7
0
00
3
4
68.1
51.9
4.02 br quint (6.3)
2.61 m
C-1; C-5
76.7
49.5
4.17 br quint (6.3)
80.0
41.5
80.0
41.5
4.30 ddt
(
12.4; 8.1; 3.7)
(13.5; 8.1; 3.6)
2.43 dd (17.0; 13.5)
2.32 dd (17.0; 3.6)
2.82 dd (16.7; 7.1)
2.56 m
2.43 dd (16.9; 12.4)
2.32 dd (16.9; 3.7)
C-2
C-6
C-2
C-6
2
.56 m
5
6
211.4
51.9
211.4
52.3
196.2
105.0
196.0
105.0
2.61 m
.56 m
2.59 m
5.23 br s
C-3; C-4; C-8
5.23 br s
C-3; C-4; C-8
2
7
8
68.1
40.5
4.02 br quint (6.3)
1.68 dt (8.1; 6.7)
C-5; C-9
C-6; C-1
68.4
40.8
4.00 br quint (6.3)
1.66 dt (8.2; 6.6)
C-5; C-9
C-1
180.0
38.0
179.9
37.9
0
0
0
0
00
00
00
00
2.56 br dt (11.4; 7.4)
C-6; C-1
C-6; C-1
2.57 br dt (10.4; 7.3)
2.55 br dt (10.4; 7.3)
2.81 br t (7.3)
C-6; C-1
C-6; C-1
00
2.54 br dt (11.4; 7.4)
00
00 00
00 00
00 00
00 00
9
32.0
2.64 m
C-7; C-2 ,6
32.2
2.62 m
2.53 dt (14.0; 8.2)
C-7; C-2 ,6
C-7; C-2 ,6
32.9
2.80 br t (7.4)
C-7; C-2 ,6
32.9
C-7; C-2 ,6
0
0
00
2
.53 m
C-2 ,6
0
1
134.2
130.4
116.2
156.5
134.2
130.4
116.2
156.5
134.7
130.7
116.5
156.7
134.5
130.7
116.4
156.6
133.2
130.4
116.3
156.7
132.4
130.4
116.2
156.9
135.7
130.4
118.0
157.7
132.4
130.4
116.3
156.9
0
0
0
0
0
0
0
0
0
0
0
0
0
2
3
4
1
2
3
4
,6
,5
7.00 br d (8.5)
6.68 d (8.5)
C-1; C-4
6.97 d (8.4)
6.65 d (8.4)
C-1; C-4
7.03 d (8.4)
6.71 d (8.4)
C-1; C-4
7.03 d (8.6)
7.13 d (8.6)
C-1; C-4
0
b
c
0
0
0
C-1
C-1
C-1
C-1
0
0
0
0
00
00
00
00
00
00
,6
,5
7.00 br d (8.5)
6.68 d (8.5)
C-9; C-4
6.97 d (8.4)
6.64 d (8.4)
C-9; C-4
6.99 d (8.4)
6.69 d (8.4)
C-9; C-4
6.99 d (8.6)
6.69 d (8.6)
C-9; C-4
00
b
c
00
00
00
C-1
C-1
C-1
C-1
b-D-Glucosyl moiety
0
0
0
0
0
0
00
00
00
00
00
00
0
1
2
3
4
5
6
103.9
75.6
78.4
72.0
78.3
63.1
4.30 d (7.7)
C-3
102.6
75.0
78.1
72.0
78.2
62.6
4.83 d (7.4)
C-4
3.11 dd (9.0; 7.7)
3.31 dd (9.0; 7.5)
3.28 m
3.27 ddd (9.5; 5.4; 2.5)
3.83 dd (11.9; 2.5)
3.39 br t (8.2)
3.44 br t (8.9)
3.39 br t (9.3)
3.43 m
3.89 dd (11.9; 2.0)
3.70 dd (11.9; 5.2)
3.66 dd (11.9; 5.4)
a
1,9-Diarylnonanoid numbering is applied to all compounds.
b,c
Values with the same superscript in one column may be interchanged.

B. Bennini et al. / Tetrahedron Letters 52 (2011) 1597–1600
1599
NMR resonances. With respect to the CO group, the outer non-
shift in the aliphatic region for the permanent oxy C-3 (d 80.0,
Dd +11.9) suggested to include this carbon in an ether linkage with
equivalent geminal protons H-1a,9a and H-1b,9b (d 2.64 and
2
.53) indeed showed two 3J correlations with the neighbouring
enhanced attractive effect and conclusively to ensure ring closure
with C-7 to lead to a 3,7-anhydroericanone-type structure. Indeed,
0
0
00 00
b-carbons C-3 or C-7 (d 68.1) and C-2 ,6 or C-2 ,6 (d 130.4). In
the same way, the inner H-3,7 (d 4.02) exhibited two J cross-peaks
3
1
the H NMR data relative to the remaining three aliphatic protons
with C-5 (d 211.4) and with either C-1 or C-9 (d 32.0) when H-2,8
(H-4a, H-4b and H-3) of the resulting disubstituted c-dihydropyr-
3
(
d 1.68) were also implicated in two J correlations with either C-4
anone ascertained these findings: H-4a (d 2.43, dd, J = 16.9 and
12.4 Hz), H-4b (d 2.32, dd, J = 16.9 and 3.7 Hz) and H-3 (d 4.30,
ddt, J = 12.4, 8.1 and 3.7 Hz). Likely flavanones — a typical example
of 2-substituted 2,3-dihydropyran-4-one — the expressed coupling
value J3,4a = 12.4 Hz clearly suggested a trans-diaxial relationship
between the two related nuclei. Consequently, the absolute config-
uration at C-3 was established as S by comparing the optical rota-
0
00
or C-6 (d 51.9) and with either C-1 or C-1 (d 134.2). Parallely, the
aromatic protons H-2 ,2 ,6 ,6 (d 7.00) gave two J cross-peaks with
either C-1 or C-9 (d 32.0) and with either C-4 or C-4 (d 156.5)
when H-3 ,3 ,5 ,5 (d 6.68) were characterized by a single J corre-
lation with either C-1 or C-1 (d 134.2). To conclude, since erica-
none is laevorotatory, it lacks symmetry between C-3 and C-7
which together must have the same configuration, that is, rel-
0
00
0
00
3
0
00
0
00
0
00
3
0
00
3
,4
tion with literature data of flavanones. Hence, the new structure
issued from the above results was (2S)-2,6-bis(p-hydroxypheneth-
yl)-2,3-dihydropyran-4-one or (3S)-3,7-anhydro-6,7-dehydroeri-
(
3R,7R) in contrast with opposite configuration only found in the
optically inactive meso-form.
1
13
canone. The detailed analysis of the H– C HMBC spectrum
supported this result and allowed unambiguous assignments for
OH
4
"
1
13
all the H and C NMR resonances and especially the discrimina-
tion of the aromatic rings through their quaternary C atoms.
1
"
9
3
0
Indeed, C-1 (d 133.2) was involved in J correlations with H-2
7
0
0
00
O
(d 2.06 and 1.91) and H-3 ,5 (d 6.71) while C-1 (d 132.4) showed
J interactions with H-8a (d 2.56) and H-3 ,5 (d 6.69). In parallel,
C-4 (d 156.7) correlated with H-2 ,6 (d 7.03) whereas C-4
d 156.9) exhibited J cross-peaks with H-2 ,6 (d 6.99). Finally,
further J correlations displayed by the latter aromatic protons,
H-2 ,6 with C-9 (d 32.9) and H-2 ,6 with C-1 (d 31.3), allowed
OR
O
OH
1
H
3
00 00
1
1'
1"
1'
3
5
7
9
3
5
O
0
0
0
00
4
'
4"
4'
HO
OH
RO
3
00 00
(
3
4
R = H
R = β-D-Glc
1
2
R = H
R = β-D-Glc
3
0
0
00
0
0
to locate each ring on the appropriate end of the partly cyclized
C chain. Biogenetically, the close relationship between this metab-
9
With a chromatographic behaviour close to that of flavonol
26
monoglycosides within this species, compound 2, ½
.015, MeOH), was also obtained as a white amorphous powder.
It was assigned the molecular formula C27 10 by HRESMS
found: 543.2201; calcd: 543.22062 for [M+Na] ). The UV spec-
a
ꢀ
ꢁ19.5 (c
D
olite and ericanone (1) seems to suggest a mutual 3-hydroxy-5,7-
diketo-type precursor involved in two distinct pathways to lead
to each one: a one-step simple reductive process of the 7-carbonyl
generating ericanone in contrast with a more extended route based
on 6,7-enolisation followed by cylization consecutive to 3,7-dehy-
dration resulting in 3,7-anhydro-6,7-dehydroericanone. In spite of
a detailed phytochemical investigation of E. cinerea, attempts at
isolating the appropriate intermediate still stay unsuccessful.
Compound 4 was also detected towards flavonol monoglyco-
sides on silica gel TLC but with a higher mobility than 2. Also iso-
lated as a white amorphous powder, it exhibited a UV spectrum
0
36
H O
+
(
MeOH
trum (kmax 280 nm) was similar to that of 1 as well as the NMR
features (Table 1) indicating a close relationship between 1 an 2.
Indeed, analysis of NMR shift values, multiplicities and coupling
constants rapidly revealed four distinct parts in 2: two quasi-
similar p-disubstituted aromatic rings, one unsymmetrical C
9
ketone and one extra hexosyl unit, all these elements suggesting
that 2 was a glycoside of 1. Indeed, mild acid hydrolysis of com-
1
pound 2 afforded glucose and ericanone (1). The remarkable
H
MeOH
consistent with one band at kmax 280 nm, and the molecular for-
1
3
and C downfield shifts of one oxymethine in 2 (H-3: d 4.17,
0.15 and C-3: d 76.7 ppm, d +8.6) indicated an ether linkage
between C-3 of the ericanone moiety and the b- -glucosyl unit
H-1 : d 4.30, d, J = 7.7 Hz). This attachment was confirmed by
the HMBC spectrum similar to that of 1 except for the additional
Dd
mula
5
27 32 9
C H O given by HRESMS (found: 523.1937; calcd:
+
D
23.19441 for [M+Na] ). Examination of the H and 13C NMR data
+
1
D
(Table 1) rapidly revealed that 4 was likely 2, a glucoside but de-
0
00
(
rived from aglycone 3. Owing to the downfield shift caused by
the ether linkage on the aglycone substituted position, attachment
3
000
J correlations observed between H-3 and the anomeric C (C-1 :
000
000
of the b-
D
-glucopyranosyl moiety (H-1 : d 4.83, d, J = 7.4 Hz; C-1 :
d 103.9) and conversely between C-3 and the anomeric proton.
Accordingly, component 2 was identified to the newly reported
0
d 102.6) was deduced to be at C-4 (d 157.7,
Dd +1.0). This result
was simultaneously confirmed by the downfield shifts assumed
ericanone 3-b-
Less polar than ericanone (1), compound 3, ½
MeOH), was also isolated as a white amorphous powder. The
molecular formula C21 was established by HRESMS (found:
39.1589; calcd: 339.15963 for [M+H] ) and once again, the UV
D-glucopyranoside.
0
0
by the ortho positions for both, protons (H-3 ,5 : d 7.13,
Dd +0.42)
2
D
7
aꢀ
+9.5 (c 0.011,
0
0
3
and C nuclei (C-3 ,5 : d 118.0,
D
d +1.7) and by the J correlation dis-
played by H-1 (d 4.83) with C-4 (d 157.7) in the HMBC spectrum
virtually identical to that of 3. Consequently, the newly reported
000
0
22 4
H O
+
3
compound 4 was established as (3S)-3,7-anhydro-3,4-dehydroeri-
MeOH
spectrum consisted of a single band at kmax 280 nm. With only
0
canone 4 -b-
D-glucopyranoside.
two isochrone phenolic functions at d 8.13 in the 1H NMR (ace-
Only nine 1,9-diarylnonanoids — mainly as open nonan-1-one
tone-d
–H O). Indeed, the comparative analysis of the C NMR of both
compounds (Table 1) pointed out in 3 an upfield shift for the keto
group (C-5: d 196.2,
d ꢁ15.2). This function was deduced to be
,b-conjugated with an electron-donating element similar to a
,7-dehydroericanone-type structure. This change was supported
6
), compound 3 differed from ericanone by 20 amu less
5–7
8,9
chain ,
rarely as cyclized chain, but never as glycosides — were
13
(
4
previously restricted to the genus Myristica (M. ceylanica, M. dac-
tyloides, M. fragrans and M. malabarica) belonging to the Myristica-
ceae, an archaic plant family when compared to the recent
D
a
6
2
Ericaceae. Conversely, with a C unit less the homologues 1,7-
diarylheptanoids are considerably more numerous. In 2002, the last
available review devoted to this group listed a total of 192 natural
3
by the pronounced downfield shift of two previous C sp converted
2
into Csp , a O-bonded quaternary C atom (C-7: d 180.0,
and a tertiary nucleus (C-6: d 105.0, d +53.1) whose proton was
shifted downfield to d 5.23. In addition, the significant downfield
D
d +111.9)
10
11–43
products. This number grew to 267 during the past decade.
D
Occuring as aglycones and/or glycosides of either 3-O-, 3,5-di-O-
or 1,3,5-tri-O-substituted linear, cyclic biphenyl or diphenyl

1
600
B. Bennini et al. / Tetrahedron Letters 52 (2011) 1597–1600
ether-type structure, 1,7-diarylheptanoids are mainly reported
from rhizome and stem bark when compared to other structural tis-
sues like heartwood, aerial parts, seeds and fruits. They are wide-
spread over thirteen plant families, namely Aceraceae, Betulaceae,
Burceraceae, Cassuarinaceae, Dioscoreacea, Fabaceae, Juglanda-
ceae, Musaceae, Myricaceae, Pinaceae, Rhoipteleaceae, Viscaceae
and Zingiberaceae. Despite a very large separating interval on the
plant evolution scale, both families Zingiberaceae (Monocotyledon)
and Betulaceae (Dicotyledon) produce the highest numbers of these
products. Similarly to their lower homologues, 1,9-diarylnonanoids
are also elaborated by the most distant Myristicaceae (Paleoplants)
and Ericaceae (Dicotyledon). Is that reflecting the translation of per-
haps a primitive and dominant character of the former, involved in
the biosynthesis of such secondary metabolites in the latter?
Atta-ur-Rahman, Ed.; Elsevier Science B.V: Amsterdam, 2002; Vol. 26, pp 881–
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